Isoamyl Nitrite → HCID 14886877, compound

HRID 1901532Notes

Reaction equation

[C:1]([O:4][C@@H:5]1[C@H:9]([O:10][C:11](=[O:13])[CH3:12])[C@@H:8]([CH2:14][O:15][C:16](=[O:18])[CH3:17])[O:7][C@H:6]1[N:19]1[CH:27]=[N:26][C:25]2[C:20]1=[N:21][C:22](N)=[N:23][C:24]=2[Cl:28])(=[O:3])[CH3:2].C(ON=O)CC(C)C.[CH3:38][S:39]SC>C(#N)C>[C:1]([O:4][C@@H:5]1[C@H:9]([O:10][C:11](=[O:13])[CH3:12])[C@@H:8]([CH2:14][O:15][C:16](=[O:18])[CH3:17])[O:7][C@H:6]1[N:19]1[CH:27]=[N:26][C:25]2[C:20]1=[N:21][C:22]([S:39][CH3:38])=[N:23][C:24]=2[Cl:28])(=[O:3])[CH3:2]

Participants

Conditions

Temperature: 100 °C

Procedure

9-(2',3',5'-Tri-O-acetyl-β-D-ribofuranosyl)-2-amino-6-chloro-9H-purine (see Example 9) (4.0 g, 9.3 mmol) was dissolved in acetonitrile (100 ml). Isoamylnitrite (10.84 g, 93 mmol) was introduced followed by methyl disulphide (4.14 ml, 46 mmol) and the reaction mixture was heated at an oil bath temperature of 100° C. for 2h. The evolved gas was removed via a hypochlorite scrubber. The reaction mixture was cooled, evaporated and purified by flash chromatography on silica gel. Elution initially with dichloromethane, followed by dichloro-methane/methanol (100/1) provided 9-(2',3',5'-tri-O-acetyl-β-D-ribofuranosyl)-6-chloro-2-methylthio-9H-purine (3.1 g, 72%) as a foam, 1H NMR (CDCl3) δ 2.12, 2.14, 2.18 (9H, 3s, 2', 3' and 5'-O-acetyl CH3), 2.66 (3H, s, --SCH3), 4.28-4.51 (3H, m, H-5'a, H-5'b and H-4'), 5.66 (1H, t, H-3'), 6.0 (1H, t, H-2'), 6.13 (1H, d, H-1'), 8.11 (1H, s, H-8).

Workup

customThe evolved gas was removed via a hypochlorite scrubber
temperatureThe reaction mixture was cooled
customevaporated
custompurified by flash chromatography on silica gel
washElution initially with dichloromethane

Sources & evidence

ORD record: ord-c7a2ec7b156a4b1ea034b9e52cffe899
Source dataset: uspto-grants-1996_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05578582

Reaction notes

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